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By James O'Brien, Lyman Frost, Grant Hawkes, S. Elangovan, Manohar Sohal, J. S. Herring, Joseph Hartvigsen, Carl Stoots

"Pressing environmental and energy security concerns have brought much needed attention to economic production of hydrogen as the secondary energy carrier for non-electrical markets as well as to meet increasing demand for crude upgrading and desulfurization. While steam reforming of natural gas is currently the dominant method of hydrogen production, it is depleting a valuable fossil fuel while emitting green house gases. Thus, in the long run, efficient, environmentally friendly, and economic means of hydrogen production using nuclear and renewable energy needs to be developed. High temperature electrolysis using solid oxide electrolyte cells is an exceptionally efficient means of generation of high purity hydrogen. It is also capable of directly converting steam and CO2 into synthesis gas. This co-electrolysis process enables conversion of CO2 recovered from concentrated industrial sources into a feedstock for synthetic fuels production. Use of CO2 provides a means of storing hydrogen in a concentrated and convenient form – a hydrocarbon. This is also an effective storage medium for intermittent renewable energy sources such as wind and solar.Ceramatec, Inc and the Idaho National Laboratory are applying solid oxide fuel cell technology to the production of synthesis gas by high temperature co-electrolysis of steam and carbon dioxide. This technology utilizes solid oxide fuel cell stacks to electrochemically remove oxygen from steam and CO2, leaving a clean stream of hydrogen and carbon monoxide suitable for fuel synthesis. By varying the relative concentrations of carbon dioxide and steam, the hydrogen to carbon monoxide product ratio can be controlled as required by the desired type of synthetic fuel being produced from the syngas. The resultant synthesis gas has been used as the feedstock to produce synthetic methane and Fischer Tropsch liquid fuels.Alkaline and proton exchange membrane electrolysis cells typically operate below 100°C, while solid oxide electrolysis cells operates in the 750-850°C range. This higher temperature improves the efficiency significantly. Practically, it translates into a lower cell operating voltage, 1.1-1.4V for high temperature electrolysis vs. ~1.8V for water electrolysis. Hydrogen production is stoichiometric with current in all types of electrolyzers.Carbon dioxide is a valuable resource as a feedstock for energy storage as a hydrocarbon. There is a vast amount of renewable energy that cannot be effectively utilized as grid electricity, but which could be used to convert CO2 to hydrocarbons, offering a solution to the even more difficult (than supplying grid power) challenge of production of sustainable, domestic transportation fuels. Conventional electrolysis and chemical processes could be deployed to accomplish this conversion. However, high temperature co-electrolysis of CO2 and steam to produce synthesis gas using solid oxide fuel cell technology has the potential of improving the efficiency by nearly 50%. A domestic synfuel industry will enable a much larger reliance on intermittent renewable energy than can be accommodated by conventional electric demand profiles while increasing our energy security."

Jan 1, 2010

By R. Shimpo

Equilibrium calculations by a computer may sometimes fail in giving solutions when the system includes a large number of components and more than three phases, and especially when no definite information about stable phases is given. An improved method of calculation is presented in which the number of phases need not to be initially fixed, phases can appear or disappear in the course of' calculation and a new method is combined with the Newton-Raphson method to obtain solutions easily. The improved method is applied to the copper smelting operation and all the successive stages of the operation are successfully simulated.

Jan 1, 1983

By C. M. Wai

"Metal species in solid and liquid materials can be extracted by supercritical carbon dioxide containing a suitable ligand. This in situ che1ation-supercritical fluid extraction technique offers several advantages over conventional solvent extraction including minimization of organic liquid waste generation and exposure of personnel to organic vapors. One unique feature of this technique is that metal species can be removed from solid materials directly using supercritical carbon dioxide as a solvent. Several ligand systems including dithiocarbamates, B-diketones, organophosphorus reagents, and macrocyclic compounds have been tested for metal extraction in supercritical carbon dioxide. This novel extraction technique may have important applications for metal recovery and mineral processing.IntroductionSupercritical fluid extraction (SFE) offers several advantages over conventional solvent extraction including the minimization of organic liquid waste generation and exposure of personnel to organic vapors.[1] The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties which make supercritical fluids excellent candidates for extraction and recovery of organic compounds from solid materials [2] Carbon dioxide is a gas of choice for SFE because of its moderate critical constants (Tc = 31 °·C and Pc = 73 atm), inertness, and availability in purified form. After extraction, the fluid phase is depressurized to separate organic solutes from CO2 gas and the gas can be recycled for repeated use. The SFE technology has been applied to industrial scale operations such as the preparation of decaffeinated coffee and hop extracts."

Jan 1, 1996

By P. Chris Pistorius

An example is presented to illustrate the joint effect of local reaction equilibria and mass transfer limitations, for reactions during ladle refining of steel. The example relies on some of the kinetic principles that David Robertson has employed to quantify many metallurgical processes. In calcium treatment of alumina inclusions in aluminum-killed steels, solid CaS forms as an intermediate reaction product. During subsequent reaction, CaS disappears and calcium aluminate forms; at the same time, aluminum and sulfur dissolve in the steel. Kinetic analysis shows that the rate of this reaction is not limited by mass transfer of dissolved aluminum and sulfur away from the reacting inclusions. The reaction rate is likely limited by transport of dissolved calcium. This example also illustrates the use of FactSage macros for kinetic modeling.

Jan 1, 2014

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothermic reduction, hydro metallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothemlic reduction, hydrometallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By Wenya Du, Qingbo Yu, Peng Li, Qin Qin

"A new heat recovery system is proposed. This system uses the endothermic heat of gasification reaction instead of sensible heat to recover the energy of molten blast furnace slag. The gasification technological parameter in molten blast furnace was calculated and the exergy of the system was analyzed. The gasification reactions were studied kinetically by the isothermal thermogravimetry using STA409PC thermal analyzer. The results showed that, according to different gasification agent, this system can produce syngas with different C-H ratio. The exergy efficiency of this system is high and its internal exergy loss rate is about 11%. This method can bring huge economic and environmental benefits which are important to the survival and sustainable development of iron-steel enterprises. The molten BF slag acts as not only thermal media but also good catalyst. The kinetic parameters on gasification reaction with different types of coal used differ from each other.IntroductionEnergy consumption in the iron-making process is about 50%~60% of the total energy input. The blast furnace is very important in the iron & steel process. So energy conservation and emission reduction about blast furnace is very important. In recent years, in order to recovery energy, many new technologies such as TRT (Top gas pressure Recovery Turbine) and CCPP (Combined Cycle Power Plant) were used in iron-making. But the energy of molten blast furnace (BF) slag has only been used limitedly so far.Molten BF (Blast Furnace) slag is the byproduct of iron-making at the high temperatures range from 1723 to 1923K, and has a large amount of sensible heat remaining. The yield of molten BF slag is about 300 kg per ton of pig iron. In conventional processes, molten BF slag is quenched rapidly using a large amount of water to produce a glassy-granulated slag. The quenching slag must be dried before it can be used in cement manufacture. During the process, a large amount of water was consumed and the energy of molten slag can not be recovered. At the same time, it causes environmental pollution problems. So the critical problems of the process are not only energy recovery of molten slag and reducing emission of H2S and SO2, but also guaranteeing the subsequent use value of slag. For this propose, many new technologies were investigated to recover the thermal energy of molten slag. The promising methods are dry granulation [1-4] and reforming of methane [5-9]. The method, utilization of reaction heat instead of latent heat and sensible heat, is quite attractive from viewpoints of energy storage without heat loss, and makes a connection to other industry. But both of them are in laboratory. In this paper, coal gasification in molten BF slag was used to recover the energy of molten BF slag. The gasification technological parameter in molten BF was calculated and the exergy of the system was analyzed. The gasification reactions were studied kinetically by the isothermal thermogravimetry using STA409PC thermal analyzer."

Jan 1, 2011

By Reza Kamali, Mohsen Bashiri, Hadi Fanisalek

"Half of the input energy to aluminum reduction cell will be lost as waste heat which could be studied for possible recovery. Since price of energy is increasing and the main production cost in primary aluminum industry is energy, so waste heat recovery consideration will be interesting. One of the possible choices for recovering is from aluminum exhaust gases that needs minimum modifications for reduction cell and has no influence on cell heat balance which is vital for the operation. By using heat exchangers with in-line and staggered tube arrangements which placed before fume treatment plant (FTP) we will be able to recover enough amount of heat. The main challenging problem which is necessary to overcome will be the heat exchanger material and its design because of corrosive and dusty exhaust gases from potroom. In this paper, a desalination system with six effects of evaporator is proposed for producing distilled water by using recovered heat from hot exhaust gases. The calculated amount of produced distilled water is around 27,000 / in this specific suggested desalination plant. The suggested desalination plant is based on Hormozgan Aluminum Company data (Hormozal) in Bandar Abbas, Iran which is constructed by the Persian Gulf.IntroductionWaste heat losses arise both from equipment inefficiencies and from thermodynamic limitations on processes. The exact quantity of industrial waste heat is poorly quantified, but various studies have estimated that as much as 20 to 50% of industrial energy consumption is ultimately discharged as waste heat [1]. In order to achieve a final decision for establishing the waste heat recovery plant in any type of industry, a strong feasibility study is mandatory. Also, we need to remember that the possible amounts of energy and suggested process plant for recovery have to be investigated before starting any feasibility study. This kind of study which is important to be finished before moving to feasibility step is mainly a theoretical study, and was done for the Hormozgan Aluminum Company (Hormozal). In addition to the exhaust gases from the potroom, the exhaust gases from anode baking plant appear to have a better potential for waste heat recovery compared to potroom exhaust gases. The average temperature of exhaust gases from anode baking kiln is 120°C higher than the exhaust gases temperature in the potroom. This needs further investigation in a different study, because this study is just focusing on potroom exhaust gases."

Jan 1, 2011

By Y. Fukunaka, M. Niinae, E. Kusaka, T. Kuzuya, R. Ishii

"Samarium oxalattr particles was precipitated in oxalic acid aqueous solution from samarium-loaded D2EHPA solution emulsified with a conventional impeller. The calculated fractional precipitation of samarium oxalate was reasonably compared with the value determined by chemical analysis. Morphological variation of oxalate precipitate particles was then examined with H2C2O4 concentration in aqueous solution, Sm(III) and D2EHPA concentrations in organic phase. The needle-like precipitate was identified as Sm2(C2O4)3 10H2O by XRD. Precipitates obtained at higher H2C2O4· or Sm(III) concentration greatly decreased the length of major axis of precipitate, while those at higher D2EHPA concentration increased it. The oxalate was further precipitated under ultrasonic irradiation. However, the morphological variation caused by theses processing variables was not so evident under ultrasonic irradiation as in an impeller or shaking mixer.IntroductionThe materials processing of the rare earth elements must be reviewed from the scope of industrial ecology, since they have the potential applications of magnetic materials as well as secondary battery in developing programs of the electric vehicle. The technological trend to develop the electric vehicle may greatly influence the concept of materials processing, since the global· environmental problem must accommodate with the sustainable development for mankind. The recycle design must be a key issue in the materials science and engineering.Solvent extraction provides a unique separation technology -in this sense. Doyle (1)(2) reported the integrating solvent extraction with processing of advanced ceramic materials, whose chemical composition and microstructure must be precisely controlled. In her paper, the higher productivity inherent to the present process superior to hydrolyzing metal alkoxides was emphasized. Oxalic acid has been used as precipitant for rare earth purification process, since rare earth oxalate has a very small solubility in water and can be easily decomposed to oxide. It is thus suitable for precipitation stripping agent in cationic exchange type extracting system (i.e. D2EHPA, VA-10, PC-88A and so on)."

Jan 1, 2000

By Ximeng Zhu

In the transpassive region, about 0.4 to 0.8 V (SCE), aggressive oxidation of pyrite occurred. The reaction products in this region were Fe(III) oxide, sulfate ion and partially oxidized sulfur intermediates. The growth kinetics of the reaction product film, resulting from transpassive oxidation of pyrite were studied using chronoamperometry measurement with both stationary and rotating disk electrodes. The effect of electrode rotation speed, solution pH and temperature were examined. Potentiostatic measurements were well correlated by a paralinear rate equation, suggesting the formation of an intermediate passive film, associated with the simultaneous dissolution of the outer layer of the film. Activation energies of 66.17 kJ/mole (15.83 kcal/mole) and 38.67 kJ/mole (9.25 kcal/mole) were obtained for associated parabolic and linear rate constants respectively, at an applied potential of 0.6 V.

Jan 1, 1993

By I. C. Howard, E. J. Palmiere

"Heat transfer and friction in hot flat rolling have traditionally been characterised by an average heat transfer coefficient (h) and an average friction coefficient (p.). However, the presence of oxide scales and asperities at the interface question the use of such averages. The apparent irregularity and lack of pattern of interactions at the interface has prompted this present investigation to move away from averaged h and 11 values, and to study their local evolution based on probabilistic rules. The approach is based on the probability of finding the workpiece surface in a specific configuration at a particular instance of time in the roll gap. These rules are based on observations of surface phenomena such as scale behaviour during hot rolling. The model is implemented using user-subroutines integrated with the commercially available finite element program ABAQUS™. The results show the strong dependence of h and u on the local scale interactions. In particular, the effect of scale thickness, material behaviour and processing conditions on the evolution of hand 11 are discussed. Finally, the development of a Cellular Automata based Finite Element (CAFE) model is proposed to model the combined interfacial phenomenon of friction and heat transfer at the tool-work piece interface.IntroductionIntricate interactions between process variables in hot rolling of steels make it a challenge to the modelling community. For a given material and geometry combination, reducing interfacial power losses can increase the efficiency of the rolling process. The roll-strip interface, therefore, forms the critical zone and is currently the domain of intense investigation, especially to characterize interfacial frictionl • 2 and heat transfer3 • 4 . These interfacial phenomena are inter-related and cannot be studied in isolation. However, very few mathematical models4 • 5 combine an analysis of friction and heat transfer and deformation of the strip-roll interface taking into account the role of asperities and oxide scales."

Jan 1, 2001

By Petrus Christiaan Pistorius, Farzin Fatollahi-Fard

The production of synthetic rutile—a common starting material for most titanium production processes—from iron-rich titanium minerals such as pseudorutile and ilmenite is described. The process for “upgrading” the mineral to synthetic rutile is by carbothermal reduction of the mineral while immersed in a molten salt at high temperature, followed by magnetic separation of the reduced iron. A variety of factors are also investigated, such as particle size of the mineral, the type of mineral, and the molten salt used. The solubility of iron(III) oxide in different molten salts is also experimentally determined.

Jan 1, 2016

By Ximeng Zhu

The electrochemical behavior of mineral and coal pyrites in stirred and quiescent alkaline boratelsulfate solutions @H 7.9-10.5) have been investigated using cyclic voltammetry. Significant differences in the electrochemical response of these pyrites were observed. At the mineral pyrite surface, three anodic peaks at about -0.8 V, -0.1 V and +0.5 V (SCE) have been detected along with their corresponding reduction peaks. The first two peaks correspond to FeIFeOI) and FeOI)lFe(III) oxidation. The third peak is present for quiescent conditions but disappears as a distinct peak when the electrolyte is stirred. In the upper voltage region +0.30V (SCE), the current increases markedly during stirring and the reactions correspond to the oxidation of pyrite with the formation FeOII) oxides plus elemental sulfur. Also there is evidence that Fe oxy-ions form. Coal pyrites, under rapid sweep conditions display only the first two anodic peaks, the associated reduction peaks and an additional reduction peak corresponding to one or more of the high voltage oxidation products. After prolonged exposure to high potentials, coal pyrite displays reactions similar to those of mineral pyrite but at much higher current densities demonstrating the much higher reactivity of the coal pyrite. The reactivity sequence was Upper Freeport coal pyrite > Pittsburgh coal pyrite > mineral pyrite.

Jan 1, 1991

By Dominik Hofer

A broad spectrum of tantalum containing input materials can be processed for the production of synthetic tantalum concentrate (“SynCon”). The use of these low grade substances offers a secure alternative to mining of coltan in Central Africa. SynCon is produced in a multi-stage pyrometallurgical process, wherefore the melting behaviour of slags presents an important factor especially regarding the energy consumption and its optimisation. The characteristics of a slag comprising mostly Al2O3, CaO, SiO2 and MgO are influenced by the amount of other oxidic constituents which enfolds the main focus of this study. A hot stage microscope serves for the investigation of the slag behaviour in a temperature range from 1000 to 1600 °C under reducing atmosphere (CO/CO2 gas). The experimental results are compared with thermodynamic calculations (FactSage) to get a better understanding of the process.

By Thomas R. Wildeman

Experimental methods for studying vapors over solid minerals are reviewed and an especially developed method using atomic absorption is described. The method is used to study vapor pressures over Te. Ag, Au, Ag2Te, and AuTe2 from 250°C through 10S0oe. Vapor pressures observed and, concurrently. sintering properties are significantly altered by the form of the solid. The vapor pressures of the tellurium compounds reveal complex processes occurring on the surfaces of the solids. The data given also point out a method of recovering precious metals from their telluride minerals w

Jan 1, 1987

By François Larouche

Since their commercialization in the early 1990s, lithium-ion batteries (LIBs) have become ubiquitous for powering a myriad of portable electronics. Their usage now extends to the automotive industry and stationary energy storage market. With an average life of 6.2 years and the strong demand, the volume of spent LIBs has increased exponentially, making recycling mandatory. Currently, recycling/ recovery of spent LIBs is limited in comparison to all other types of batteries. The current processes focus mainly on the recovery of the most valuable metals such as cobalt and nickel, leaving lithium and phosphate in a low value end-product. It is necessary that new advanced recycling technologies are developed for the recovery of spent LIBs both from an economic and environmental perspective. In this paper, the current R&D status of LIBs recycling is reviewed with the emphasis placed on hydrometallurgical processing opportunities for Li-ion and Li-solid state batteries.

By Jerold L. Johnson

Remediation of small-arms firing ranges is being investigated by the Naval Civil Engineering Laboratory and the U.S. Bureau of Mines. Scheduled closures of military installations, as well as the management of active ranges, require the development of methodologies for heavy metals removal to prevent their entering the surrounding environment. The impact berms contain high concentrations of metals, and the soil and vegetation surrounding the berms were found to have slightly elevated levels. The heavy metals characterized are in the form of whole bullets, a wide size distribution of free fragments, smeared lead on the surface of the soil grains, and very finely attached particles. Gravity beneficiation can remove liberated metal contamination effectively. Weak acetic acid leaching shows promise in lowering the final metal contamination to allow the ,soil to pass the Environmental Protection Agency's (EPA) Toxicity Characteristic Leaching Procedure (TCLP) criteria.

Jan 1, 1993

By Zhucheng Huang, Lingyun Yi, Bin Chai, Tao Jiang

"A high iron content manganese ore was reduced at 900~1200°C and followed by a magnetic separation process. SEM and EDS analyzes were employed to examine the transformation of microstructure and phase in reduced sample and the mechanism was revealed. Results showed that elements enriched during reduction. Iron existed in the metal iron phase and most of oxygen formed compound with manganese. Consequently a clear distinguish between iron phase and manganese minerals formed, which was beneficial to the separation of iron and manganese. But the iron phase can not be monomer dissociation in grinding process and manganese compounds turned into magnetic product as package and mechanic inclusion due to the isomorphism of iron and manganese and the small particle size. And MnO could be found partially in iron phase, which hindered the further separation of manganese and iron.IntroductionManganese is widely used in industry. The amount of manganese used in steel industry is very huge and 90% manganese is used in steel industry. Manganese ore resources are rich in China, yet with fewer rich ore but more low-grade ore which accounts for 93.6% and fine refractory ore. The constitution of the ore is very complex and more than 73% of all the manganese ore contains iron[l,2]. With the increasing of consumption of steel, the demand for manganese is becoming larger and larger and the imported ore accounts for more than 50%. Therefore, how to use the manganese ore efficiently has very significant meaning. The main method is manganese residual, which is simple and stable. However, the development of the method is limited by the quality of manganese ore, the huge amount of manganese residual, the technology of blast furnace process and economics[3,4]. Chemical benefication which may pollute environment and is difficult to recover iron is still being researched[5,6]. The paper investigated the process in which anthracite coal was the reducing agent for coal-based direct reduction and magnetic separation of the ore, and SEM with EDS measurements were employed to examine the transformation of phase in reduced sample and the mechanism was revealed[7,8]."

Jan 1, 2013

By M. Wallin

Millions of tons of sludge from different metallurgical processes are produced worldwide annually, and the environmental impact of landfilling these often hazardous sludges stresses the need to understand their role as valuable resources. The current work explores the potential of producing a saleable low-phosphorous ferromanganese alloy by utilizing sludge from the silicomanganese industry together with an iron source. The aim of the project is to explore the feasibility and practical challenges related to reduction and dissolution of manganese and silicon from the sludge to liquid metal and slag. Parameters such as ratio of input material as well as the effect of adding limestone and coke to the mixture were explored by thermodynamic calculations and adapted experimentally. Results show that a ferromanganese alloy, in fact, can be formed, while silicon and calcium forms a complex slag that captures a significant amount of impurities.

By Andriy Burbelko, Daniel Gurgul, Wojciech Kapturkiewicz, Marcin Gómy

"The mathematical model of the globular eutectic solidification in 2D was designed. The proposed model is based on the Cellular Automaton Finite Differences (CA-FD) calculation method. The model has been used for studies of the primary austenite and of globular eutectic grains growth during the ductile iron solidification in the thin wall casting. The model mentioned above takes into account, among other things, non-uniform temperature distribution in the casting wall cross-section, kinetics of the austenite and graphite grains nucleation, solute diffusion and non-equilibrium nature of the interphase boundary migration.Some aspects of stochastic nature of the solidification processes are taken into account. The results of the CA solidification modeling have been shown, that differences between cooling curves obtained in the same conditions of the casting solidification may be a result of the stochastic nature of the grain nucleation.The results of modeling were compared with the experimental microstructure. The model is well worked for thin walled ductile iron casting, for fast solidification process.IntroductionNodular graphite cast iron, also known as ductile iron (DI), has major applications in critical engineering parts due to its mechanical properties and castability. The mechanical and physical properties of this material depend on the shape and number of the graphite grains andmicrostructure of the metallic matrix.Solidification of DI was a subject of many computer modeling programs described in literature [ 1-5], in which the stationary conditions of carbon diffusion in austenite is pre-assumed. Recently, a tendency for production of thin-walled castings has been observed [ 6-8]. In this technology, the process of the fast solidification may be very far from equilibrium and steadystate conditions [9].The purpose of the present work is a two-dimension model development for simulation of the DI structure formation during the solidification in the condition of non steady-state temperature and diffusion fields in the thin-wall casting.Model of process The CA-FD is one of the known methods of the simulation ofmicrostructure formation during the solidification [ 10, 11]. In the CA microstructure modeling the outer grain shape is the result of the simulation and does not superimposed beforehand. The model development for a onephase microstructure evolution is a subject of the numerous researches [12 -23]. Model of the eutectic solidification of DI in the uniform temperature field and superimposed cooling rate is known [24]."

Jan 1, 2013